Novel benzimidazoles

ABSTRACT

in which R1 and R2 are identical or different and are each alkyl, alkenyl, cycloalkyl, cycloalkylalkyl or alkylcycloalkyl, alkoxyalkyl and alkylthioalkyl, carboalkoxyalkyl, cyanoethyl, phenyl, benzyl or phenylethyl, R1 in addition is alkoxy, and R1 and R2 together are alkylene optionally interrupted by O, S, &gt;NCH3, &gt;N-CH2H5 or substituted by methyl or ethyl groups or bridged by a methylene group, are especially valuable systemic fungicides. Benzimidazoles of the formula

United States Patent [1 1 Rochling et al.

[4 1 Sept. 9, 1975 NOVEL BENZIMIDAZOLES [75] Inventors: Hans Rochling, Altenhain, Taunus;

Kurt Harte], Hofheim, Taunus; Helmut Goebel, Frankfurt am Main all of Germany [73] Assignee: Hoechst Aktiengesellschaft;

Frankfurt am Main, Germany [22] Filed: June 19, 1973 [21] Appl. No.: 371,537

[30] Foreign Application Priority Data June 21, 1972 Germany 2230182 [52] US. CL... 260/247.2 B; 260/243 B; 260/268 BC; 260/251 R; 260/293.54; 260/293.6;

[51] Int. Cl. C07C 295/04 [58] Field of Search 260/247.2 B, 309.2, 268 H, 260/268 BC, 243 B, 293.54

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 1.5 23,597 5/1968 France Primary Examiner-Robert G-erstl Assistant Examiner-Paul J Killos Attorney, Agent, or FirmCurtis, Morris & Safford 5 7 ABSTRACT Benzimidazoles of the formula I -NH-COOCHU 11 Claims, N0 Drawings NOVEL BENZIMIDAZOLES in which R and R are identical or different and are each alkyl having 1 to l8 carbon atoms, alkenyl having 3 to 18 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, cycloalkylalkyl or alkylcycolalkyl having 5 to 6 carbon atoms in the ring and l to 3 carbon atoms in the alkyl or alkylene moiety, alkoxyalkyl and alkylthioalkyl having 2 to 12 carbon atoms altogether, carboalkoxyalkyl having 3 to 9 carbon atoms altogether, cyanoethyl, phenyl, benzyl or phenylethyl, R, in addition is alkoxy having 1 to 4 carbon atoms, and R and R together are alkylene having 4 to 7 carbon atoms optionally inter rupted by O, S, N--CH NC H or substituted by methyl or ethyl groups or bridged by a methylene group.

The compounds of formula I are prepared by reacting 2-methoxycarbonylamino-benzimidazole of the formula ll @N/ NH COOCH II with a secondary amine of the formula III I HN\R2 III and formaldehyde. In preferred embodiment of the process of theinvention, the Z-methoxycarbonylamino-benzimidazole II) is suspended or dissolved in a solvent, a"oneto two molar amount of the amine is added and, while stirring, a one to four molar amount of aqueous formaldehyde solution is added. Instead of aqueous formaldehyde solution, gaseous formaldehyde may also be used. The reaction is preferably carried out at temperatures of from 0 to 80C, the temperature range being, however, not critical. Normally, the end products are dissolved in the reaction mixture and thus can be separated from unreacted Z-methoxycarbonylamino-benzimidazole by filtration. They are isolated in pure form by concentrating the remaining solution and treating it with an inert solvent. for example gasoline, or by recrysallization, for example from methylene chloride/gasoline.

Besides the amines used in the examples the following amines are suitable, cited by way of examples:

Diisopropylamine. di-sec-butylamine, diphentylamine, dihexylamine, diheptylamine, dioctylamine, di tert-octylamine, dinonylamine, diisononylamine, didecylamine, diundecylaminc, didodecylamine, ditridccylamine, ditetradecylamine, dipentadecylamine,

dihexadecylamine, diheptadecylamine, dioctadecylamine, N-'propyl-N -propoxy-arnine, N-butyl-N-butoxyamine, Nallyl-N-methylamine, N-allyl-N-ethylamine, N-allyl-N-propylamine, N-allyl-N-butylamine, N-benzyl-N-ethylamine, N-benzyl-N-propylamine, N-benzyln-butylamine, N-( 2-cyanoethyl)N-ethylamine, N-( 2- cyanoethyl )-N-n-propylamine, N-( 2-cyanoethyl )-N- isobutylamine, N-(2-cyanoetlhyl)-N-dodecylamine, N- (2-cyan oethyl )-N-isotridecylamine, N-( 2-cyanoethyl N-hexadecylamine, N-(2-cyanoethyl)-N- octadecylamine, N-(( 2-carboethoxy-ethyl )-N- methylamine, N-( 2-carbomethoxy-ethyl )-N- methylamine, N-( 2-carbomethoxy-ethyl )-N-nbutylamine, n-propyl-isooctylamine, n-propylisononylamine, isobutyl-isononylamine, cyclohexyl-3- methyl-butylamine, cyclohexyl-isononylamine, diisotridecylamine, N-methylQN-cyclohexylamine, N- allyl-N-methylamine, N-oleyl-IN-methylamine, N-oleyl- N-ethylamine, di-oleylamine, N-methoxyethyl-N- methylamine, di-(methoxyethyD-amine, N-butoxyethyl-N-ethylamine, N-ethylthioethyl-N-methylamine, diphenylamine, di-(phenylethyl)-amine, di-(4-methylcyclohexyl )-amine, di-( 4-isopropyl-cyclohexyl )-amine, di-(cyclohexylmethyl)-amine, N-ethyl-piperazine, heptamethyleneimine, 2,6-dimethyl-pyrimidine, 4- methylpyrimidine.-

The solvents suitable for the reaction are preferably moderately or slightly polar solvents having a low boiling point, for example methylene chloride, chloroform, carbon tetrachloride, benzene; ethers such asdiethyl ether, diisopropyl iether, and tetrahydrofurane; esters such as methyl acetate and ethyl acetate; or ketones such as acetone or methylethy] ketones; chloroform or methylene chloride being preferred.

Z-Methoxycarbonylamine-benzimidazole can be prepared by the method described in J. Am. Chem. Soc. 56, page 144 (i934) by reacting o-phenylene diamine with S-methyLisothiourea dicarboxylic acid-dimethyl ester. The preparation of the amines used for the reaction is likewise known from literature.

The compounds of the invermtion have a good fungicidal, especially systemic effect against plant fungi, which permits a curative control of fungi that have already penetrated into the planttissue. This is especially important with fungus diseases having a long incubation time which cannot becombated with the conventional fungicides after infestation. The range of action of the novel compounds is= -very broad, they are effective against a number of important fungi causing diseases in crop forming, fruit *g'rowing, vine growing, hop growing, gardening, and the growing of ornamental plants. There are mentioned by-. way of example:

Fusicladium, Glocosporium, Cylindrosporium, Botyrtis, Verticillium, Ce'rcospora, Septoria, Mycosphaerella, Cladosporium, Colletotrichum, Rhizoctonia, Fusarium, Cercosporella, Ustilagineae, Erysiphaceae, Aspergillaceae, Sclerotinaceae.

Moreover, some of the novel compounds, especially those having long chain radicals R, have an excellent effect against phycomycetes which are unsusceptiblc to other known benzimidazole type fungicides such as Peronospora and Phytophthora. Their efiiciency in this respect is equal and sometimes even superior to that of the known dithiocarbamates or the N-trichloromethylthiophthalimide derivatives which are presently used against these types of fungi.

The compounds of the invention canalso be used for the-protection of stored fruit and vegetables against infestation-with fungi (for example Fusarium, Penicillinium and other types) and in the technical field, for example to protect textiles,'wood, dyestuffs and paints for rot fungi and other fungal organisms.

The fungicides containing the aminoalkylbenzimidazoles of formula I have a concentration of from 2 to 95 percent of .active ingredient in admixture with the usual formulation additives such as solid or liquid inert carrier materials, adhesives, wetting and dispersion agents and/or grinding auxiliaries. They can be used in theform ofwettable powders, emulsions, suspensions, dusts, orgranules. The compositions may be mixed with other fungicides with which they form compatible mixtures.

Suitable carrier materials are mineral substances,'-for example, aluminiumsilicates, argillaceous earths, kaolimchalk, siliceous chalk, talc, kieselguhr, and bydrated silicic acid, or preparations of thise material substances with special additives, for example chalk with:sodium stearate. I I

Carrier materials-for'liquid preparations are all suitable .and commonorganic solvents,-for example toluene, xylene, diacetone alcohol, cyclohexanone, isophorene, gasoline, paraffin oils, dioxane, dimethyl formamide, *dimethylsulfoxide, ethyl acetate, tetrahydrofurane; andchlorobenzene. 1

{Asadhesivesrthere can be used-glutinous cellulose productsmr, polyvinylalcohols.

:As wettingagents there can be used all suitable emulsifiers,; for example oxethylated alkylphenols, salts of aryl .or 'alkylaryl sulfonic acids, salts of oleyl-methyltaurine, salts of oxethylated phenylsulfonic acids, andsoaps: v

Suitable dispersion media are celluloses waste liquor (salts of lignin sulfonic acid), salts of. naphthalenesulfonic'acid, and salts of-oleyl-methyl-taurine.

As grinding auxiliaries, suitable inorganic or organic salts can be used, forexample sodium sulfate, ammo nium sulfate,.sodium carbonate, sodium bicarbonate, sodium thio'sulfate, sodium stearate, and sodium acetate. 1 v

The,- compounds of formula I can 'be used further as anthelmintic agents in veterinary medicine for combating parasitic-diseases of warm blooded animals, especially ..;helminths. They exhibit an especially pronounced anthelmintic activity, combined with a good compatibility against :strong yles parasitic in the alimentary tract, mainly of ruminants-3 Theseparasites may cause great economical damage in-.a'nimal breeding. Hence, the-compounds of the invention-represent valuable medicines. ln practice, the anthelmintic agents are administered orally or subcutaneously.- For oral administrationready-prepared suspensions (1 to 50 percent, preferably .3 to percent strength), water suspendable powders (concentration 1 to 80 percent, preferably 40 to 70 percent), pastes or granules of different concentrations are used. For parenteral treatment sterile solutions of different concentrations are suitable. To achieve a good distribution, stabilization and conservation of the active" ingredient, as well as an improvedresorption, additives are necessary, preferably'talc,'la

tos'e, magnesium stearate, finely dispersed silicic acid starch and polyethylene glycol.

The following examples illustrate the invention.

bonylamino-benzimidazole were suspended in 600 ml of methylene chloride, 17.4 g (0.2 mole) of morpholine were added 'and. the mixture. was heated to'35C. At

that temperature, 30 ml (0.33 mole) of aqueous formaldehyde solution of. 35 percent strength were added dropwise, whereby the temperature rose to 38C. Stirring was continued for an hour at 38C, the mixture was allowedto cool whilestirring, the unreacted 2-methoxycarbonylamino-benzimidazole was filtered off with suctionjthe filtrate dried over magnesium sulfate and concentrated at about 36C under reduced pressure. The solid residue was dissolved and precipitated using methylene chlorid'e/n-hexane.

l2 Grams of 1 morpholinomethyl-2-methoxycarbonylamino-benzimidazole were obtained melting at l76l77C. v I H EXAMPLE 2 I 57.3 Grams (0.3 mole) of Z-methoxycarbonylaminebenazimidazole were suspended in 900 ml of methylene chloride, 18.3 g (0.3 mole) of N-methylmethoxyamine were added, the mixture was heated to 30C and, while stirring, 43 ml (0.5 mole) of 35 percent aqueous formaldehyde solution were dropped in. Stirring was continued for 2 hours at 38C, the mixture was allowed to cool while stirring, and the unreacted'2-methoxycar bonylamino-benzimidazole was filtered off with suction. The water was separatedfrom the filtrate, the methylene chloridephas'e dried over magnesium sulfate, filtered and concentrated at 35C under reduced pressure. a a v To eliminate adhering'amine impurities the residue was stirred with 200. ml of gasoline (30/85C). 19.84 Grams of E 5 l (N-rn ethoxy-N-methylaminomethyl)-2- methoxycarbonylamino-benzimidaZole melting at 202C were obtained. v

The compounds of the formula indicated in the following table were prepared in the manner described in Examples 1 and 2.

TABLE TABLE-Continued Example R I Melting Example 2R Melting No. I point "C No.- I poi'nt C CH; 3 lxu-lsv z s C -H l 5 i 7 206 207 CHH- CH n .28 "167-168 6 -N J 203-205 C4H9 n C H iso I 7 -N/ 4 q 102mm H C.,H,, iso C H- iso i x N w 145-!63 CmH iso B. Examples of Application CH; 9 EXAMPLE 1 C3"? v Winter wheat in the four-leaf stage was sprayed to 0 210-211 the dri -off with the com ounds accordin to Exam \C H I P P g k" ples 3, 2, 9, l5, 1 l, 4, 22-, 5, 6, 7 andwS, each'in concen u -N 81:89 trations of 120, 60, 30, 15, 7.5, and 3.75 mg of active gr Y ingredient per liter of spray liquor. The experiment was 12 176498 repeated four times. Ascomparative Compound beno- CHr-GH; myl (methyl-l (butylcarbamoyl)r2-bcnzimidazole can bamate) wasmsed in the same concentrations After CH drying of the spray liquor the, plants were stronglyvi fested with conidia of wheat mildew (Erysiphe gram-v i 13 N oil not mm) and placedm the greenhouse at 80-9O percent of dislillflhlc relative atmospheric humidity and,-20 -,-22 C. V s After an incubation time of l4days, the plants were examined by visual inspection as to the degree ofjnfes- I tatlon w th m ldew. The degree of nfestation is ex- 14 N -l96-|99 pressedan 70 0f infested leaf surface, comparedw thuntreated and, infested control plants; 15 W648; The results summarized inTable 1 indicate that the \CHQCH2CN compounds of the invention had a verygood effect I I 6 V 1170475 equal or even superior to that of benomyl.

\CH- .--CH- .-,CN v

CH, EXAMPLE ll 17 CH 124425 Kidne be ns of he variety Andreas were thoroughly 2, LIHZCH2'C mixed for ID minutes in a drum with the compounds of Exam les 23, 24, 25, l, and 26, the concentrations 18 N 200-202 p \CH,CH2CN being 100, 50, 25, 12.5, 6.25 and 3.0 g of active Ingredient for 100 kg of seeds. As comparative agent beno- 1 my] was used in the's'ame concentration. 19 N\ 196-198 After a time of action of'24 hours, IO be'ans each n were sown'in pots filled with earthfstfrongly infested 20 --N 9 180-182 with Rhiioctonia solani causing rhizocto nia. The ex-j periments were repeated 5 times. The'po'ts were then /C1H: n s a i "'1 2] placed in the greenhouse. 6 Weeks aftcrsowlng, the. -C 1 i germinated plants were counted and the "efi'ic ieric'y of 27 2084") the test compounds was determined in percent of \OC2H;, healthy plants. The results indicated in Table [I show that'the com: 23 O 244L343 pounds of the invention had an excellent efi'ectagainst Rhizoctonia solani equal or even superior tothat of" benomyl. 34 -N 198-200 i I EXAMPLE I]! g V M Sugar beet plants in the six-leaf stage were strongly 7 N *8 I infested with conidia of Cercospora beticola causing 65 leaf spot and placed in a climatic chamber having a rel-- ative atmospheric humidity'of I percent and a temperature of 25C, After an infestation time of 2 days the 36 172-177 plants'were transferred into the greenhouse'where they in.-the "same concentration.

7 weie kept for 6"days at a temperature of 2S Z6C and a high relative atmospheric humidity of 80-90 percent. Tlieplants were then sprayed to the .drip'-oif, withthe compounds listed in Example l in a concentration of 1520, 60, 30115, 7.5, 3.75 mg of active ingredient per liter of's pray liquor. Each experiment was" carried out 4 times. As comparative agent benomyl was used After drying of the spray liquor, the plants were again brought into the greenhouse where they were kept until the development'of the disease. The degree of infestation was evaluated by visual inspection. lt is expressed in Table lll'in percent of infested leafsurface, calculated on the basis of untreated but infested control plants. It can be seen from the table that the compounds of the invention had a very good curative effect equal or even superior to that of the comparative agent.

EXAMPLE lV Winter wheat of the variety Heine Vll was thoroughlymixed for 10 minutes in a vibrating drum with .the compoundslisted in- Example II, the concentration garden earth, 1.0 seeds in each pot in 5 repetitions, and

thepotswere placed in'the greenhouse.

As soon as the'gerrninated plants had developed the third or fourth leaf,they= were strongly infested with conidia of= mildew of wheat and the conditions in the greenhouse were adjusted to 80-90 percent ofatmospheric moisture and 22-23C. After an incubation time'of 14 days the plants were examined as to their infestation with mildew and the degree of infestation was determined'in'percent of infested leaf surface, calculated on the basis of untreated but infested control plants.

The results indicated inTable lV shows that the compounds of the invention had a good systemic effect and in'general prevented the infestation with mildew better than the comparative agent.

; EXAMPLE V In a vibrating drum garden earth was thoroughly strongly infested in the 4-leaf stage with conidia of mildew of wheat (Erysiphe graminis) and the conditions .in the greenhouse were adjusted to 80-90 percent of atmospheric moisture and 20-22C, i.e. optimum growing conditions for the fungus.

After an incubation time of 14 days, the plants were examined by visual inspection as to their infestation with mildew and the degree of infestation was determined in percent of infested leaf surface, calculated on the basis of untreated but infested control plants.

The result indicated in Example V shows that the compounds of the invention had a systemic effect which was generally better than that of the comparative agent.

i EXAMPLE VI The tips of apple seedlings of the variety Golden Delicious in the 6 -leaf stage were pinched off, the lower older 2 leaves were removed and the plants were strongly infested with a suspension of conidia of Fusicladium dentriticum. The infested plants were kept dripping wet for 2 days in a climatic chamber having a relative humidity of 100 percent and a temperature of 20C. Next, they were placed in the greenhouse at 18C and a relative atmospheric humidity of -95 percent. After an infestation time of 5 days, the plants were treated'withthe compounds of Examples 23, 24, 25, and 1, respectively, the concentrations being 60, 30, 15, 7.5, 3.75, and 1.9 mg of active ingredient per liter of spray liquor. Each experiment was repeated 4 times. As comparative agent benomyl was used in the same concentrations.

After drying of the spray liquor, the plants were transferred again into the greenhouse where they remained until examination of the degree of infestation by visual inspection after a time of incubation of 3 weeks. The degree of infestation is expressed in percent of infested leaf surface, calculated on the untreated but EXAMPLE vn Rice plants in the 4-leaf stage were treated with the compounds listed in Example I in concentrations of 60, 30, 15, 7.5, 3.75 and 1.9 mg of active ingredient per liter of spray liquor, each experiment being repeated 4 times. As comparative agent benomyl was used in the same concentrations. After drying of the spray liquor, the plants were strongly infested with Piricularia oryzae causing 'leaf spot and placed in a climatic chamber at percent of relativehumidity and.25C.

, After a residence time of 24 hours in the climatic chamber, the plants were transferred into the greenhouse having a temperature of 25C to 26C and a high relative humidity of 80-90 percent. After an incubation time of l4'days, the plants were examined by visual inspection as to their infestation with Piricularia. The degree of infestation is indicated in Table VI] in percent of infested leaf surface in comparison to untreated but infested control plants.

The results show that the compounds of the invention had a very good fungicidal effect which was better than that of the comparative agent.

EXAMPLE Vlll Tomato plants of the variety Rheinlands Ruhm were strongly infested in the grown up 3-leaf stage with conidia' of Cladosporum fulvum causing leaf mould and thenplaced in a climatic chamber at 25C and 100 percent relative humidity. 'After24 hours, the plants were transferred into' the greenhouse having a relative humidity of 80-90 percent and a temperature of 25-26C. I

After'a time of infestation of 5 days, the plants were sprayed drip wet with the compounds listed in Example I, the concentrations being 60, 30, I5, 7.5, 3.75, and

1.9 mg of active ingredient per liter of spray liquor. As comparative agent benomyl was used in the same concentrations. I 1

After drying of the spray liquor, the plants were replaced into the greenhouse and after an incubation time of 21 days, they were examined as totheir infestaof the comparative agent.

EXAMPLE IX Oat seeds of the variety Flamin gsgold strongly infested artificially with Ustilago avenea causing loose smut of oats were treated for minutes in a vibrating drum with the compounds listed in Example II and benomyl as comparative agent, respectively, the concentrations being 60, 30, 15, 7.5, 3.75 and 1.9 g of active ingredient for 100 kg of seeds. 1

After a time of action of 24 hours '10 se edseach were sown in pots filled with earth, in 5 repetitions, and the pots were placed in the greenhouse. 1

After shooting, the panicles infested with loose smut were counted. The results indicated in Table IX show that the compounds of the invention had an excellent effect against Ustilago avenea generally superior to that of benomyl. I I

EXAMPLE X being 500. 250, 125, 60, 30, and mg of active ingre-, dient per liter of spray liquor. Each experiment was re-- peated 4 times. As comparative agents bcnomyI:(-l) and folpet (II) were used in the same concentrations.

fested with a suspension of zoosporangia of Peronos- 1 10' having. a temperature of 22C; and a re latiye humidity of 8590 percent.

After an incubation time of 14 days, the plants'were examined by visual inspection as to the degree of infes tation' with Oidium, given in percent of infested leaf surface in comparison to untreated. but infested'control After drying of the spray liquor the plants werefin- -4 pora viticola and placed in a chamber at a relative humidity of 100percent and a temperature of 20C. After 24 hours the plants were transferred into the green house at 25C and 80-90 percent relative humidity.

After an incubation time of 7 days the wetted plants; were placed over night into the moisture chamber to 1 cause the disease to break out. The degree of infestation was determined by visual inspection and is indicated in Table X in percentof infested leaf surface in comparison with untreated but infested control plants.

The results indicated in Table X show that the compounds of the invention had a very good effect against A Peronospora which was equal to that of the comparative agent II (folpet), whereas comparative agent I (benomyl) was ineffective against the fungus.

EXAMPLE XI listed in Example X, the concentrations being 20, '10,

5, 2.5, 1.25, and 0.6 mg of active ingredient per liter of spray liquor. As comparative agents benomyl (I) and folpet (II) were used.

After drying of the spray liquor, the plants were strongly infested with conidia of powdery mildew of vine (Oidium tuckeri) and placed in the greenhouse plants. V t I The results indicated in TabIeXI show that thecor'rh pounds of the invention had the same excellent effect as benomyL in part they were e ven superior. ln eornparison folpetrwhich is well effective against Perono'spora, even in high concentrations I exhibited only a weak but absolutely insufficient effect against oidium.

EXAMPLE XII Tomatoplants of the variety Bonner'Beste. were treated, in the 3-leaf stage with the compounds listed.

quor, the plants were strongly' infested with a-.-suspe'nsion of zoosporangia of Phytophthora infestan's' and kept for one day in a climatic chamber. at IOOpercent of relative humidity and 15C. Then they were:transferredinto a coldgree'nhouse at a temperatureof 15C and a relativehumidity of 85-95 percent.

After an incubation time of 7 days, the plantswere examined as to their infestation with Phytophthora; the

degree of infestation being expressed in percent of in-- fested' leaf surface. calculated on the untreated but infested control plants. The results are indicated inTabIe XII.- p f TABLE I" infestation with mildewot wheat with Compound ingot active ingredientper liter of x of spray liquor I t v Example 120 30 I5 7.5 3.7 5

3 0 0 a 17K 25 2' 0 (I 5 I0 21, 28 9 I 0 =0 ='5 12 20 27 I5 0 0 .2" 7 I5 23 l 1 0 0 5 I I0 16 25 4 0 6 I2 21 30 40 22 0 5 10" 1s 27 36 5 0. 1 0 .,.5. A 12 t8 28 a 0 I 3 to 7 I6 25 31-, 7 0 s s l5 26 34 s 0 10 15 25 30] 42 hcn'omyl 0 s l5 7 V 23 3| .45 p I I00 I00 i00 I00 I00 I00 '1 untreated infested control plants TABLE II- Com'pound '71 cfficicncy against R/lizucmniu with g of of active ingredient for l00 kg ofseeds. Example I00 50 25 12.5 6,25 3.0

23.. 100- 100 95 so 70 24 I00 I00 1.00 .90. t 85 25 I00 I00 90 85 70 I 100 I00' I00 95 '85 26 I00 1 100 )5 80 70 bcnomyl m0. 90 s5 so 70 so untreated 0 0 0 v 0 0 0 seeds in infested soil TABLE iii TABLE vii i -tat ign wit h (f r 'p r1 with fi f Compound infestation with Piriz'illariu with mg of Compound 'irigredient p rliter of spray of active ingredient l liter of pm) of lic 'uor v N 5 Example liquor Example 120 6(-):: 30 15 7.5 a 3.75 15 3 I 0 v 0 3 8 l7 3 O O 2 8 15 2| Li 1 2' O O 5 8 14 23 2 (J O 5 l2 2] 1 u 9 i .0 3 w 6 l5 2l 9 (l O 0 3 l0 l8 v 15 O O r;5. 4'10 l6 23 l5 0 O 5 12 2O 10 H 0 5 18 24 ll 0 O O J 8 l5 23 4 0 8 2] 30 4 O (l 5 l() l7 28 22 U 8 112 20 29 22 O O 6 l2 l8 3() 5 O 0 3 1O 14 24 5 O I O 8 14 25 6 0 0 5 2 18 25 6 O (J 3 l0 l) 28 7 0 0 7 5 20 2 7 I, 0 0 5 l2 I8 30 g 0 5 '10 29 3 8 Y I 0' (l 3 15 23 39 benomyl 0 5 l0 2l 3 42 henomyl O l0. l7 38 *5 100 I00 v 100 100 100 [O0 3') 10 0 100 y l 100 100 lOO I untreated infested 'control'plants untre'ated infested control plants t I a 20 TABLE viii TABLE IV V I Compound infestation with Claclmpurium fuli'um Compound infestation with rnildew after seed of l mg 9 uctvc 'ngrcd'cm P of treatment with g of active ingredient Example 'gg H 7 5 3 75 l 9 Example for l()() kg of seeds v 25- 200 l()() 50 25 l2.5 6.25 i I t 3 O O 5 l2 I3 25 l 2 U 0 3 l0 I8 28 23 U, 0 8 12 2O 28 9 U 0 2 '5 24 24 0 9 5 m 25 l5 0 0 24 I4 21 30 25 0 0 x i5- 21 30 E 0 m 17 25 I 0 3 8 34 30 4 0 2 8 I6 20 30 4 226 v 0 5 l2 IX 25 36 22 0 3 8 I8 2 29 Enemy 1 0 10 15 21 34 5 0 0 5 l0 I8 24 untreated I00 v 100 I00 I00 100 I00 6 3 g 14 23 30 3 i i infested 7 O 5 l0 I6 24 3! control plants 8 0 8 I5 21- 2) 38 henomyl 3 l0 18 25 31 45 IOU l()() 100 l[)() l()() l()() V untreated infested controlplants Compound 7 infestation with mildew of wheat with 40 TABLE 1 of mg of active ingredient per liter of z l t Ex lmplc spmylgluur 5 25 L25 046 03 Compound of panieles infested with g of active of ingredient per kg of seeds Example 6O 3O 15 7.5 3.75 [.9 '23 (l i i 0 .8 15 23 28 24 O O 5 12 20 25 3 O O 0 3 2 28 25 0 0 s I4 21 2x 24 0 0 0 O 5 18 l 0 5 25 25 0 0 .0 5 l8 3| 26 0 3 8 15 25 34 l 0 (i .0. 0 5 i2 henomyl I Q 5 l0 l8 27 39 l 2 Q 5 2 2| infested me 100 100 100 m0 100 hcnomyl u 0 3 i0 18' 35 control plants untreated 85 80 4 79 '86 84 2 in untreated infested oat earth seeds TABLE VI TABLE x I v v Compound 71 infestation with Fuxiclzulium with mg Comlmund leaf f fll f l v of of active ingredient per liter of of w th mg ot JLKHL' ingredient per liter Example p y liquur Example oi spray liquor v 30" '5 3'75 "9 500 -50 I25 6U 30 l5 7 60 g u u x I5 21 3o 23 (l (l 5 l() I5 28 H 0 5 m 20 24 (l (l 3 l0 18 23 cumpunnivc 3 x 35 agent! 100 100 um um mu 100 l U U E 8 comparative bcnvmyl 0 0 1 l 21 36 agent" 0 u '5 I2 18 30 untreated I untreated I00 I00 I00 l(-)t) 100 l()() infested I00 l()() I00 100- 5 I00 I00 infested con trol plants control plants TABLE XI Compound infestation with ()idium of vine with of of active ingredient per liter of spray Example liquor 1* s o a 16 23 '32 39 ll 3 l0 18 ,26 '35 comparative agent I 0 5 I2 25 30 4o comparative agent ll 30 95 I00 100 l()() 100 untreated 100 I00 I00 l()() 100 l ()0 infested a control plants TABLE Xll Compound "/1. of infestation with Plrvmphmru with mg of of active ingredient per liter of spray Example liquor 500 250 l 25 6O 3O 8 (l 2 l0 I8 30 42 l l 0 (l 6 I8 25 36 comparative agent l 100 l()() l()() I00 I00 I00 comparative agent ll 0 0 8 i5 28 4() untreated I00 H10 I00 I00 I00 I00 infested control plants What is claimed is: l. A benzimidazole of the formula I -NH--COOCH; I l N/ I l R! CH-;N

in which R and R are identical or different and are each alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 18 carbon atoms, cycloalkyl having 4 to 8 carbon atoms cycloalkylalkyl or alkylcycloalkyl having 5 to 6 carbon atoms in the ring and l to 3 carbon atoms in the alkyl or alkylene moiety, alkoxyalkyl and alkylthioalkyl having 2 to 12 carbon atoms altogether, carboalkoxyalkyl having 3 to 9 carbon atoms altogether, cyanoethyl, phenyl, benzyl or phenylethyl, R in addition is alkoxy having I to 4 carbon atoms, and R and R together are alkylcnc having 4 to 7 carbon atoms optionally interruptcd by O, S, N-CH,;, NC H or substituted by methyl or ethyl groups or bridged by a methylene group.

2. A compound as claimed in claim 1 which is 3. A compound as claimed in claim 1 which is 5. A compound as claimed] in claim 1 which is 6. A compound as claimed in claim 1 which is 7. A compound as claimed in claim 1 which is 8. A compound as claimed in claim I which is 9. A compound as claimed in claim 1 which is H cu u 10. A compound as claimed in claim 1 which is 11. A benzimidazolc of the formula in which R is alkoxy of l to 4 carbo'fi atoms or R and R are identical or different and are alk'yl of l to 18 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 4 to 8 carbon atoms, cycloalkylalkyl or alkylcycloal- 5 ky] of 5 to 6 carbon atoms in the ring and 1 to 3 carbon atoms in the alkyl or alkylcne moiety, alkoxyalkyl or alkylthioalkyl of 2 to 12 carbon atoms. 

1. A BENZIMIDAZOLE OF THE FORMULA 1
 2. A compound as claimed in claim 1 which is
 3. A compound as claimed in claim 1 which is
 4. A compound as claimed in claim 1 which is
 5. A compound as claimed in claim 1 which is
 6. A compound as claimed in claim 1 which is
 7. A compound as claimed in claim 1 which is
 8. A compound as claimed in claim 1 which is
 9. A compound as claimed in claim 1 which is
 10. A compound as claimed in claim 1 which is
 11. A benzimidazole of the formula 